Living/controlled ring-opening (co)polymerization of lactones by Al-based catalysts with different sidearms

It remains a challenging task to synthesize well-defined multi-block copolymers through the controlled/living ring-opening polymerization (ROP) of lactones without transesterification, the most common side reaction occurring during copolymerization. A series of Al-based complexes with different sidearms were prepared for living ROP of lactones such as ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) in the presence of BnOH at room temperature (RT), affording medium to high molecular weight (MW) linear polyesters with Mw up to 303 kg mol-1 and narrow molecular weight distributions (MWD, Đ as low as 1.12). The coordination-insertion polymerization mechanism was proposed based on the combination of the detailed experimental data and polymerization kinetics. It should be noted that the sidearm plays a significant important role in the reactivity of these Al-based catalyst systems. More specifically, the Al2 system with a butyl substituent on the sidearm exhibited the highest polymerization activity and the Al5 system with the bulkiest sidearm showed the lowest one among the investigated catalysts. Moreover, the Al4 system with a pyridine group on the sidearm could effectively inhibit transesterification and maintain a well-defined block copolymer structure even after heating at 50 °C for 10 h, which could also be confirmed by chain-end analyses of the produced polymers with the MALDI-TOF MS measurement.